CN114784236B - Coated Al and F co-doped monocrystalline lithium manganate positive electrode material and preparation method and application thereof - Google Patents
Coated Al and F co-doped monocrystalline lithium manganate positive electrode material and preparation method and application thereof Download PDFInfo
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims description 37
- 238000005303 weighing Methods 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 17
- 238000000713 high-energy ball milling Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 6
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000013543 active substance Substances 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 23
- 238000001514 detection method Methods 0.000 description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000005056 compaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910018626 Al(OH) Inorganic materials 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a coated Al and F co-doped monocrystalline lithium manganate positive electrode material, and a preparation method and application thereof, and belongs to the technical field of preparation of battery positive electrode materials. The preparation method comprises the following steps: firstly, doping elements Al and F are introduced into beta-MnO by a planetary ball milling mode 2 In which the doped beta-MnO is formed by sintering 2 And then doping beta-MnO 2 Mixing a lithium source with a coating agent, and performing secondary sintering to obtain the monocrystalline lithium manganate anode material. According to the invention, specific elements are adopted to dope and coat the lithium manganate, so that the crystal structure of the lithium manganate anode material can be stabilized, and the dissolution of Mn and side reaction between active substances and electrolyte are inhibited, thereby improving the specific capacity, initial charge and cycle performance of single-crystal lithium manganate.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a coated Al and F co-doped monocrystalline lithium manganate positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries are widely used in portable electronic devices because of their high voltage, high energy density, long cycle life, and the like. With the development of new generation information technology, new energy, energy conservation, environmental protection, digital creative and other emerging industries, the lithium ion battery is changed to the electric automobile and large-scale energy storage field, and the safety and the manufacturing cost of the battery are important points of attention in the fields.
The positive electrode material is the core and key material of lithium ion battery. The lithium manganate has the advantages of abundant reserves, low material cost, high safety and the like, and is one of the most widely applied anode materials at present. However, in the practical application process, the cycle performance, the high-temperature performance and the rate discharge performance of lithium manganate are all required to be further improved, otherwise, the capacity exertion of the material is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a lithium manganate positive electrode material which is simple in process, easy to control and low in cost, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
coated Al and F co-doped monocrystalline lithium manganate positive electrode material with chemical formula [ Li ] x Al a Mn b (O 4-c/2 F c )]·[N d O e ] f The single crystal lithium manganate comprises a lithium manganate core Li x Al a Mn b (O 4-c/2 F c ) And N d O e A coating layer;
wherein x is more than or equal to 1.00 and less than or equal to 1.05,0.001, a is more than or equal to 0.050, b is more than or equal to 1950 and less than or equal to 1.999, a+b=2, and d and e satisfy N d O e Valence balance, f < 0.1; n (N) d O e Selected from La 2 O 3 、Y 2 O 3 、ZrO 2 、Cr 2 O 3 、ZnO、Bi 2 O 3 、TiO 2 、MgO、B 2 O 3 、Nb 2 O 5 And V 2 O 5 At least one of them.
Particle diameter D of the single crystal lithium manganate 50 Is 8-12 μm.
A coated Al and F co-doped single crystal lithium manganate positive electrode material comprises the following steps:
(1) Weighing manganese source and Al (OH) according to stoichiometric ratio 3 And LiF, taking deionized water as a solvent and a polyalcohol substance as an emulsifier, mixing and ball-milling 6 and h in a planetary ball mill to prepare uniform slurry;
(2) Granulating by a spray dryer, and then drying at 120 ℃;
(3) Sintering for 6-12 hours at 500 ℃ in air atmosphere to obtain a doped manganese source;
(4) Weighing a lithium source, a doped manganese source and a coating agent N according to stoichiometric ratio d O e Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor; n (N) d O e Selected from La 2 O 3 、Y 2 O 3 、ZrO 2 、Cr 2 O 3 、ZnO、Bi 2 O 3 、TiO 2 、MgO、B 2 O 3 、Nb 2 O 5 And V 2 O 5 At least one of (a) and (b);
(5) And sintering at a high temperature of 700-850 ℃ for 12-24 hours in an air atmosphere to obtain the monocrystal lithium manganate anode material.
The polyalcohol substance in the step (1) comprises any one or a combination of at least two of PEG, PVA or PPG.
The lithium source of step (1) comprises any one or a combination of at least two of an oxide, hydroxide, carbonate or acetate of lithium.
The manganese source in the step (1) is beta-MnO 2 Particle diameter D 50 Is 4-6 μm.
The coated Al and F co-doped monocrystalline lithium manganate positive electrode material is applied to a positive electrode plate of a lithium ion battery.
By adopting the technical scheme, compared with the prior art, the invention has the following positive effects:
1. the lithium manganate is prepared by adopting a two-step sintering method, and firstly, doping elements are introduced into beta-MnO by adopting a planetary ball milling mode 2 In which the doped beta-MnO is formed by sintering 2 And then doping beta-MnO 2 Mixing the lithium source and the coating agent for sintering, so that the mixing unevenness and phenomenon of materials can be effectively reduced, and meanwhile, the mixing discharge phenomenon of lithium can be reduced;
2. lithium manganate is doped by anions and cations of Al and F, the bond energy of an Al-O bond is far greater than that of an Mn-O bond, the stability of a material structure is improved, and the electrolyte LiPF is restrained by a fluorinated surface formed by F 6 Inhibit the formation of HF and improve the interface stability of the material. The crystal lattice distortion caused by doping can be reduced by the cooperation of the lithium manganate and the crystal structure of the lithium manganate anode material is stabilized;
3. the double modification of doping and cladding improves the stability of the inside and the interface of the single crystal lithium manganate material, can fully inhibit lattice distortion caused by the Jahn-Teller effect in the charge-discharge process, further improves the normal temperature cycle performance and the multiplying power discharge performance of the material, and ensures that the material has higher gram capacity and longer cycle life.
In conclusion, the lithium manganate battery anode material has high safety, good stability and good storage and circulation performance at high temperature, prolongs the service life and reduces the cost; has the advantages of high gram capacity, high compaction density, long normal temperature cycle life good rate discharge performance, good high-temperature electricity storage performance and the like.
Drawings
FIG. 1 is an SEM image of the positive electrode material obtained in example 1;
FIG. 2 is a graph showing the particle size of the positive electrode material obtained in example 1;
FIG. 3 is a charge-discharge curve of the positive electrode material obtained in example 1;
FIG. 4 is a plot of the rate performance of the lithium manganate battery of example 1;
FIG. 5 is a graph of cycling performance of the lithium manganate battery of example 1;
FIG. 6 is an SEM image of the positive electrode material obtained in example 2;
fig. 7 is an SEM image of the positive electrode material obtained in example 4.
Detailed Description
The invention is further described in connection with the drawings and detailed description which are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a coated Al and F co-doped single crystal lithium manganate, wherein the chemical general formula of the single crystal lithium manganate is [ Li ] 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 )]·[Nb 2 O 5 ] 0.01 The single crystal lithium manganate comprises a lithium manganate core Li 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 ) And Nb (Nb) 2 O 5 And a coating layer.
The embodiment also provides a preparation method of the monocrystalline lithium manganate positive electrode material, which comprises the following steps:
(1) Weighing beta-MnO according to the molar ratio Al to Mn to F=0.02 to 1.98 to 0.01 2 、Al(OH) 3 And LiF, taking deionized water as a solvent and PEG2000 as an emulsifier, mixing and ball milling 6 and h in a planetary ball mill to prepare uniform slurry;
(2) Granulating by a spray dryer, controlling the solid-to-liquid ratio to be 1:1.2, controlling the air outlet temperature to be 120 ℃, controlling the feeding speed to be 20 mL/min, and then drying at 120 ℃;
(3) Sintering 6h at 500 deg.C in air atmosphere, cooling, pulverizing and sieving to obtain doped beta-MnO 2 ；
(4) Weighing LiOH and Li according to the molar ratio of Li to Mn to Nb=1.02 to 1.98 to 0.02 2 CO 3 Doped beta-MnO 2 And a capping agent Nb 2 O 5 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(5) Sintering 16 h at 800 ℃ in air atmosphere to obtain the monocrystal lithium manganate anode material [ Li ] 1.03 Al 0.02 Mn 1.98 (O 3.995 F 0.01 )]·[Nb 2 O 5 ] 0.01 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: adhesive=8:1:1, a metal lithium sheet is used as a negative electrode sheet, an R2032 type battery is prepared for testing, a new wire tester is adopted, and under the charging and discharging system of charging to 4.3V and discharging to 3.0V, the detection is carried out, wherein the 1C discharging gram capacity is 118.1mAh/g, and the compaction density of the electrode sheet is as follows: 3.0g/cm 3 The capacity retention rate is 83.4% after 1000 weeks of normal temperature circulation.
Example 2
The embodiment provides a preparation method of the monocrystalline lithium manganate positive electrode material, which comprises the following steps:
(1) Weighing beta-MnO according to the molar ratio Al to Mn to F=0.01 to 1.99 to 0.01 2 、Al(OH) 3 And LiF, taking deionized water as a solvent and PEG4000 as an emulsifier, mixing and ball-milling 6 and h in a planetary ball mill to prepare uniform slurry;
(2) Granulating by a spray dryer, controlling the solid-to-liquid ratio to be 1:1.2, controlling the air outlet temperature to be 120 ℃, controlling the feeding speed to be 20 mL/min, and then drying at 120 ℃;
(3) Sintering 9 h at 500 deg.C in air atmosphere, cooling, pulverizing and sieving to obtain doped beta-MnO 2 ；
(4) Weighing Li according to a molar ratio of Li to Mn of La=1.02:1.99:0.02 2 O, doped beta-MnO 2 And a coating agent La 2 O 3 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(5) Sintering at a high temperature of 780 ℃ in air atmosphere for 18 h to obtain the single crystal lithium manganate anode material [ Li ] 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 )]·[La 2 O 3 ] 0.01 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: adhesive=8:1:1, a metal lithium sheet is used as a negative electrode sheet, an R2032 type battery is prepared for testing, a new wire tester is adopted, and under the charging and discharging system of charging to 4.3V and discharging to 3.0V, the detection is carried out, wherein the 1C discharging gram capacity is 117.5mAh/g, and the compaction density of the electrode sheet is as follows: 3.0g/cm 3 The capacity retention rate is 81.3% after 1000 weeks of normal temperature circulation.
Example 3
The embodiment provides a preparation method of the monocrystalline lithium manganate positive electrode material, which comprises the following steps:
(1) Weighing beta-MnO according to the molar ratio Al to Mn to F=0.01 to 1.99 to 0.01 2 、Al(OH) 3 And LiF, mixing and ball milling 6h in a planetary ball mill by taking deionized water as a solvent and PPG as an emulsifier to prepare uniform slurry;
(2) Granulating by a spray dryer, controlling the solid-to-liquid ratio to be 1:1.2, controlling the air outlet temperature to be 120 ℃, controlling the feeding speed to be 20 mL/min, and then drying at 120 ℃;
(3) Sintering 12h at 500 deg.C in air atmosphere, cooling, pulverizing and sieving to obtain doped beta-MnO 2 ；
(4) Weighing LiOH and doped beta-MnO according to the molar ratio of Li to Mn to Zr=1.02 to 1.99 to 0.02 2 Coating agent ZrO 2 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(5) Sintering 24h at 750 ℃ in air atmosphere to obtain the monocrystal lithium manganate anode material [ Li ] 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 )]·[ZrO 2 ] 0.02 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: adhesive=8:1:1, a metal lithium sheet is used as a negative electrode sheet, an R2032 type battery is prepared for testing, a new wire tester is adopted, and under the charging and discharging system of charging to 4.3V and discharging to 3.0V, the detection is carried out, wherein the 1C discharging gram capacity is 117.8mAh/g, and the compaction density of the electrode sheet is as follows: 3.0g/cm 3 The solution is circulated for 1000 weeks at normal temperature, and the capacity retention rate is 82.1%.
Example 4
The embodiment provides a preparation method of the monocrystalline lithium manganate positive electrode material, which comprises the following steps:
(1) Weighing beta-MnO according to the molar ratio Al to Mn to F=0.01 to 1.99 to 0.01 2 、Al(OH) 3 And LiF, taking deionized water as a solvent and PEG2000 as an emulsifier, mixing and ball milling 6 and h in a planetary ball mill to prepare uniform slurry;
(2) Granulating by a spray dryer, controlling the solid-to-liquid ratio to be 1:1.2, controlling the air outlet temperature to be 120 ℃, controlling the feeding speed to be 20 mL/min, and then drying at 120 ℃;
(3) Sintering 7 h at 500 deg.C in air atmosphere, cooling, pulverizing and sieving to obtain doped beta-MnO 2 ；
(4) Weighing Li according to a molar ratio of Li to Mn to Cr=1.02 to 1.99 to 0.02 2 CO 3 、Li 2 O, doped beta-MnO 2 And coating agent Cr 2 O 3 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(5) Sintering 14 h at 780 ℃ in air atmosphere to obtain the single crystal lithium manganate anode material [ Li ] 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 )]·[Cr 2 O 3 ] 0.01 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: bondingThe reagent=8:1:1, a metal lithium sheet is used as a negative electrode sheet, an R2032 type battery is prepared for testing, a Xinwei tester is adopted, and under the charging and discharging system of charging to 4.3V and discharging to 3.0V, the detection is carried out, the 1C discharging gram capacity is 117.5mAh/g, and the compaction density of the electrode sheet is: 3.0g/cm 3 The solution is circulated for 1000 weeks at normal temperature, and the capacity retention rate is 82.2%.
Example 5
The embodiment provides a preparation method of the monocrystalline lithium manganate positive electrode material, which comprises the following steps:
(1) Weighing beta-MnO according to the molar ratio Al to Mn to F=0.01 to 1.99 to 0.01 2 、Al(OH) 3 And LiF, taking deionized water as a solvent and PVA as an emulsifier, mixing and ball milling 6 and h in a planetary ball mill to prepare uniform slurry;
(2) Granulating by a spray dryer, controlling the solid-to-liquid ratio to be 1:1.2, controlling the air outlet temperature to be 120 ℃, controlling the feeding speed to be 20 mL/min, and then drying at 120 ℃;
(3) Sintering at 500 deg.c in air at 10 h deg.c, cooling, crushing and sieving to obtain doped beta-MnO 2 ；
(4) Weighing LiOH and Li according to the molar ratio of Li to Mn to Bi=1.02 to 1.99 to 0.02 2 O、CH 3 COOLi, doped beta-MnO 2 And a coating agent Bi 2 O 3 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(5) Sintering 17 h at 790 ℃ in air atmosphere to obtain the monocrystal lithium manganate anode material [ Li ] 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 )]·[Bi 2 O 3 ] 0.01 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: adhesive=8:1:1, a metal lithium sheet is used as a negative electrode sheet, an R2032 type battery is prepared for testing, a new wire tester is adopted, and under the charging and discharging system of charging to 4.3V and discharging to 3.0V, the detection is carried out, wherein the 1C discharging gram capacity is 117.3mAh/g, and the compaction density of the electrode sheet is as follows: 3.0g/cm 3 The capacity retention rate is 82.4% after 1000 weeks of normal temperature circulation.
Example 6
The embodiment provides a preparation method of the monocrystalline lithium manganate positive electrode material, which comprises the following steps:
(1) Weighing beta-MnO according to the molar ratio Al to Mn to F=0.01 to 1.99 to 0.01 2 、Al(OH) 3 And LiF, mixing and ball milling 6h in a planetary ball mill by taking deionized water as a solvent and PEG10000 as an emulsifier to prepare uniform slurry;
(2) Granulating by a spray dryer, controlling the solid-to-liquid ratio to be 1:1.2, controlling the air outlet temperature to be 120 ℃, controlling the feeding speed to be 20 mL/min, and then drying at 120 ℃;
(3) Sintering 11 h at 500 deg.C in air atmosphere, cooling, pulverizing and sieving to obtain doped beta-MnO 2 ；
(4) Weighing Li according to a molar ratio of Li to Mn to Zr=1.02 to 1.99 to 0.02 2 O, doped beta-MnO 2 Coating agent ZrO 2 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(5) Sintering at 800 ℃ in air atmosphere at a high temperature of 14 h to obtain the single crystal lithium manganate anode material [ Li ] 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 )]·[ZrO 2 ] 0.02 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: adhesive=8:1:1, a metal lithium sheet is used as a negative electrode sheet, an R2032 type battery is prepared for testing, a new wire tester is adopted, and under the charging and discharging system of charging to 4.3V and discharging to 3.0V, the detection is carried out, wherein the 1C discharging gram capacity is 117.4mAh/g, and the compaction density of the electrode sheet is as follows: 3.0g/cm 3 The capacity retention rate is 82.8% after 1000 weeks of normal temperature circulation.
Example 7
The embodiment provides a preparation method of the monocrystalline lithium manganate positive electrode material, which comprises the following steps:
(1) Weighing beta-MnO according to the molar ratio Al to Mn to F=0.01 to 1.99 to 0.01 2 、Al(OH) 3 And LiF, mixing and ball milling 6h in a planetary ball mill by taking deionized water as a solvent and PPG as an emulsifier to prepare uniform slurry;
(2) Granulating by a spray dryer, controlling the solid-to-liquid ratio to be 1:1.2, controlling the air outlet temperature to be 120 ℃, controlling the feeding speed to be 20 mL/min, and then drying at 120 ℃;
(3) Sintering at 500 deg.c in air at 10 h deg.c, cooling, crushing and sieving to obtain doped beta-MnO 2 ；
(4) Weighing Li according to a molar ratio of Li to Mn to Y=1.02 to 1.99 to 0.02 2 CO 3 LiOH, doped beta-MnO 2 And a coating agent Y 2 O 3 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(5) Sintering at 850 ℃ in air atmosphere at a high temperature of 12h to obtain the single crystal lithium manganate anode material [ Li ] 1.03 Al 0.01 Mn 1.99 (O 3.995 F 0.01 )]·[Y 2 O 3 ] 0.01 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: adhesive=8:1:1, a metal lithium sheet is used as a negative electrode sheet, an R2032 type battery is prepared for testing, a new wire tester is adopted, and under the charging and discharging system of charging to 4.3V and discharging to 3.0V, the detection is carried out, wherein the 1C discharging gram capacity is 116.9mAh/g, and the compaction density of the electrode sheet is as follows: 3.0g/cm 3 The capacity retention rate is 82.3% after 1000 weeks of normal temperature circulation.
Comparative example 1
The comparative example provides a preparation method of a monocrystal lithium manganate positive electrode material, and the preparation method does not carry out the early-stage beta-MnO 2 Directly synthesizing the monocrystal lithium manganate anode material by a one-step method. The preparation method comprises the following steps:
(1) Weighing Li according to the molar ratio of Li to Al to Mn to F to Nb=1.03 to 0.02 to 1.98 to 0.01 to 0.02 2 CO 3 、LiOH、β-MnO 2 、Al(OH) 3 LiF and coating agent Nb 2 O 5 Performing high-energy ball milling on the mixture 3 and h to obtain a lithium manganate precursor;
(2) Sintering 16 h at 800 ℃ in air atmosphere to obtain the monocrystal lithium manganate anode material [ Li ] 1.03 Al 0.02 Mn 1.98 (O 3.995 F 0.01 )]·[Nb 2 O 5 ] 0.01 。
And (3) electrical property detection: the formula of the positive plate adopts active substances: conductive agent: adhesive=8:1:1, and metal lithium sheet is used as a negative electrode sheet to prepare an R2032 type battery for testing, wherein the new wire is adoptedThe tester detects that the 1C discharge gram capacity is 114.2mAh/g under the charging and discharging system of charging to 4.3V and discharging to 3.0V, and the pole piece compaction density is as follows: 3.0g/cm 3 The capacity retention rate is 78.6% after 1000 weeks of normal temperature circulation.
The above description is not intended to limit the present invention, but is not limited to the above examples, and variations, modifications, additions or substitutions within the spirit and scope of the present invention will become apparent to those of ordinary skill in the art.
Claims (5)
1. The preparation method of the coated Al and F co-doped monocrystalline lithium manganate anode material is characterized by comprising the following steps of:
(1) Weighing manganese source and Al (OH) according to stoichiometric ratio 3 Mixing and ball milling LiF with deionized water as solvent and polyalcohol as emulsifier in a planetary ball mill for 6 hr to obtain homogeneous slurry;
(2) Granulating by a spray dryer, and then drying at 120 ℃;
(3) Sintering for 6-12 h at 500 ℃ in air atmosphere to obtain a doped manganese source;
(4) Weighing a lithium source, a doped manganese source and a coating agent N according to stoichiometric ratio d O e Performing high-energy ball milling for 3 hours to obtain a lithium manganate precursor; n (N) d O e Selected from La 2 O 3 、Y 2 O 3 、ZrO 2 、Cr 2 O 3 、ZnO、Bi 2 O 3 、TiO 2 、MgO、B 2 O 3 、Nb 2 O 5 And V 2 O 5 At least one of (a) and (b);
(5) Sintering at a high temperature of 700-850 ℃ for 12-24 hours in an air atmosphere to obtain the monocrystal lithium manganate anode material;
the chemical general formula of the monocrystalline lithium manganate anode material is [ Li ] x Al a Mn b (O 4-c/2 F c )]·[N d O e ] f The single crystal lithium manganate comprises a lithium manganate core Li x Al a Mn b (O 4-c/2 F c ) And N d O e A coating layer;
wherein x is more than or equal to 1.00 and less than or equal to 1.05,0.001, a is more than or equal to 0.050,1.950, b is more than or equal to 1.999, a+b=2, and d and e satisfy N d O e Valence balance, f < 0.1; n (N) d O e Selected from La 2 O 3 、Y 2 O 3 、ZrO 2 、Cr 2 O 3 、ZnO、Bi 2 O 3 、TiO 2 、MgO、B 2 O 3 、Nb 2 O 5 And V 2 O 5 At least one of (a) and (b); particle diameter D of the single crystal lithium manganate 50 8 μm to 12 μm.
2. The preparation method of the coated Al and F co-doped single crystal lithium manganate positive electrode material as claimed in claim 1, which is characterized by comprising the following steps: the polyalcohol substance in the step (1) comprises any one or a combination of at least two of PEG, PVA or PPG.
3. The preparation method of the coated Al and F co-doped single crystal lithium manganate positive electrode material as claimed in claim 1, which is characterized by comprising the following steps: the lithium source of step (1) comprises any one or a combination of at least two of an oxide, hydroxide, carbonate or acetate of lithium.
4. The preparation method of the coated Al and F co-doped single crystal lithium manganate positive electrode material as claimed in claim 1, which is characterized by comprising the following steps: the manganese source in the step (1) is beta-MnO 2 Particle diameter D 50 4-6 μm.
5. The coated Al and F co-doped monocrystalline lithium manganate positive electrode material prepared by the preparation method of the coated Al and F co-doped monocrystalline lithium manganate positive electrode material is applied to a positive electrode plate of a lithium ion battery.
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